U.S. patent application number 12/373588 was filed with the patent office on 2010-01-14 for catalytic isomerization between e and z isomers of 1,2,3,3,3-pentafluoropropene.
This patent application is currently assigned to E.I. DuPont De Nemours and Company. Invention is credited to Mario Joseph Nappa, Donald J. Toton.
Application Number | 20100010277 12/373588 |
Document ID | / |
Family ID | 38690539 |
Filed Date | 2010-01-14 |
United States Patent
Application |
20100010277 |
Kind Code |
A1 |
Nappa; Mario Joseph ; et
al. |
January 14, 2010 |
Catalytic Isomerization Between E and Z Isomers of
1,2,3,3,3-Pentafluoropropene
Abstract
A process is disclosed to increase the Z/E ratio of
1,2,3,3,3-pentafluoropropene. The process involves contacting a
starting material comprising 1,2,3,3,3-pentafluoropropene with a
catalyst on AlF.sub.3 or carbon, wherein the catalyst is selected
from the group consisting of SbCl.sub.wF.sub.5-w,
TiCl.sub.xF.sub.4-x, SnCl.sub.yF.sub.4-y and TaCl.sub.2F.sub.5-z
wherein w is from 0 to 4, x is from 0 to 3, y is from 0 to 3, z is
from 0 to 4, to obtain a product wherein the Z/E ratio of
1,2,3,3,3-pentafluoropropene is increased relative to the Z/E ratio
of 1,2,3,3,3-pentafluoropropene in the starting material. A process
is also disclosed to decrease the Z/E ratio of
1,2,3,3,3-pentafluoropropene. The process involves contacting a
starting material comprising 1,2,3,3,3-pentafluoropropene with a
catalyst on AlF.sub.3 or carbon, wherein the catalyst is selected
from the group consisting of SbCl.sub.wF.sub.5-w,
TiCl.sub.xF.sub.4-x, SnCl.sub.yF.sub.4-y and TaCl.sub.zF.sub.5-z
wherein w is from 0 to 4, x is from 0 to 3, y is from 0 to 3, z is
from 0 to 4, to obtain a product wherein the Z/E ratio of
1,2,3,3,3-pentafluoropropene is decreased relative to the Z/E ratio
of 1,2,3,3,3-pentafluoropropene in the starting material.
Inventors: |
Nappa; Mario Joseph;
(Newark, DE) ; Toton; Donald J.; (New Castle,
DE) |
Correspondence
Address: |
E I DU PONT DE NEMOURS AND COMPANY;LEGAL PATENT RECORDS CENTER
BARLEY MILL PLAZA 25/1122B, 4417 LANCASTER PIKE
WILMINGTON
DE
19805
US
|
Assignee: |
E.I. DuPont De Nemours and
Company
|
Family ID: |
38690539 |
Appl. No.: |
12/373588 |
Filed: |
July 11, 2007 |
PCT Filed: |
July 11, 2007 |
PCT NO: |
PCT/US07/15752 |
371 Date: |
February 23, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60830940 |
Jul 13, 2006 |
|
|
|
Current U.S.
Class: |
570/166 |
Current CPC
Class: |
C07C 17/358 20130101;
C07C 17/358 20130101; B01J 27/135 20130101; C07C 21/18 20130101;
B01J 27/12 20130101 |
Class at
Publication: |
570/166 |
International
Class: |
C07C 19/08 20060101
C07C019/08 |
Claims
1. A process comprising: contacting a starting material comprising
1,2,3,3,3-pentafluoropropene with a catalyst supported on AlF.sub.3
or carbon, wherein said catalyst is selected from the group
consisting of SbCl.sub.wF.sub.5-w, TiCl.sub.xF.sub.4-x,
SnCl.sub.yF.sub.4-y and TaCl.sub.zF.sub.5-z wherein w is from 0 to
4, x is from 0 to 3, y is from 0 to 3, z is from 0 to 4, to obtain
a product wherein the Z/E ratio of 1,2,3,3,3-pentafluoropropene is
increased relative to the Z/E ratio of 1,2,3,3,3-pentafluoropropene
in said starting material.
2. The process of claim 1 wherein the Z/E ratio of
1,2,3,3,3-pentafluoropropene in said product is at least 10.
3. (canceled)
4. (canceled)
5. The process of claim 1 wherein 1,2,3,3,3-pentafluoropropene in
said starting material is E-1,2,3,3,3-pentafluoropropene.
6. The process of claim 1 wherein said contact is conducted at a
temperature of from about -20.degree. C. to about 150.degree.
C.
7. (canceled)
8. (canceled)
9. (canceled)
10. A process comprising: contacting a starting material comprising
1,2,3,3,3-pentafluoropropene with a catalyst supported on AlF.sub.3
or carbon, wherein said catalyst is selected from the group
consisting of SbCl.sub.wF.sub.5-w, TiCl.sub.xF.sub.4-x,
SnCl.sub.yF.sub.4-y and TaCl.sub.zF.sub.5-z wherein w is from 0 to
4, x is from 0 to 3, y is from 0 to 3, z is from 0 to 4, to obtain
a product wherein the Z/E ratio of 1,2,3,3,3-pentafluoropropene is
decreased relative to the Z/E ratio of 1,2,3,3,3-pentafluoropropene
in said starting material.
11. The process of claim 10 wherein 1,2,3,3,3-pentafluoropropene in
said starting material is Z-1,2,3,3,3-pentafluoropropene.
12. (canceled)
13. The process of claim 10 wherein said contact is conducted at a
temperature of from about 300.degree. C. to about 450.degree.
C.
14. The process of claim 1 wherein said catalyst is SbF.sub.5.
15. (canceled)
16. (canceled)
17. The process of claim 1 wherein said catalyst is
TiCl.sub.xF.sub.4-x, wherein x is from 0 to 3.
18. (canceled)
19. (canceled)
20. The process of claim 1 wherein said catalyst is
SnCl.sub.yF.sub.4-y, wherein w is from 0 to 3.
21. (canceled)
22. (canceled)
23. The process of claim 1 wherein said catalyst is
TaCl.sub.zF.sub.5-z wherein z is from 0 to 4.
24. (canceled)
25. (canceled)
26. The process of claim 10 wherein said catalyst is SbF.sub.5.
27. The process of claim 10 wherein said catalyst is
TiCl.sub.xF.sub.4-x, wherein x is from 0 to 3.
28. The process of claim 10 wherein said catalyst is
TaCl.sub.zF.sub.5-z wherein z is from 0 to 4.
29. The process of claim 10 wherein said catalyst is
SnCl.sub.yF.sub.4-y, wherein w is from 0 to 3.
Description
BACKGROUND
[0001] 1. Field of the Disclosure
[0002] The disclosure herein relates in general to processes for
the catalytic isomerization between E and Z isomers of
1,2,3,3,3-pentafluoropropene (HFC-1225ye).
[0003] 2. Description of Related Art
[0004] As a result of the Montreal Protocol phasing out ozone
depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons
(HCFCs), industry has been working for the past few decades to find
replacement refrigerants. The solution for most refrigerant
producers has been the commercialization of hydrofluorocarbon (HFC)
refrigerants. The new hydrofluorocarbon refrigerants, HFC-134a
being the most widely used at this time, have zero ozone depletion
potential and thus are not affected by the current regulatory phase
out as a result of the Montreal Protocol. The production of other
hydrofluorocarbons for use in applications such as solvents,
blowing agents, cleaning agents, aerosol propellants, heat transfer
media, dielectrics, fire extinguishants and power cycle working
fluids has also been the subject of considerable interest.
[0005] There is also considerable interest in developing new
refrigerants with reduced global warming potential for the mobile
air-conditioning market.
[0006] HFC-1225ye, having zero ozone depletion and a low global
warming potential, has been identified as a potential refrigerant.
HFC-1225ye can also find use in other applications such as
solvents, cleaning agents, foam blowing agents, aerosol
propellants, heat transfer media, dielectrics, fire extinguishing
agents, sterilants and power cycle working fluids. HFC-1225ye may
also be used to make polymers. HFC-1225ye may exist as one of two
configurational isomers, E or Z, which boils at different
temperatures. Depending on the applications, HFC-1225ye may be
preferably used as a Z isomer or a E isomer or a mixture thereof.
The liquid phase SbF.sub.5 catalyzed isomerization of E-HFC-1225ye
to Z-HFC-1225ye has been described by Burton et al. in Journal of
Fluorine Chemistry, 44, 167-174 (1989).
[0007] There is a need for new catalytic isomerization processes
for the isomerization between E-HFC-1225ye and Z-HFC-1225ye.
SUMMARY
[0008] A process has been provided to increase the Z/E ratio of
HFC-1225ye. The process comprises: contacting a starting material
comprising HFC-1225ye with a catalyst supported on AlF.sub.3 or
carbon, wherein said catalyst is selected from the group consisting
of SbCl.sub.wF.sub.5-w, TiCl.sub.xF.sub.4-x, SnCl.sub.yF.sub.4-y
and TaCl.sub.zF.sub.5-z wherein w is from 0 to 4, x is from 0 to 3,
y is from 0 to 3, z is from 0 to 4, to obtain a product wherein the
Z/E ratio of HFC-1225ye is increased relative to the Z/E ratio of
HFC-1225ye in said starting material.
[0009] A process has also been provided to decrease the Z/E ratio
of HFC-1225ye. The process comprises: contacting a starting
material comprising HFC-1225ye with a catalyst supported on
AlF.sub.3 or carbon, wherein said catalyst is selected from the
group consisting of SbCl.sub.wF.sub.5-w, TiCl.sub.xF.sub.4-x,
SnCl.sub.yF.sub.4-y and TaCl.sub.zF.sub.5-z wherein w is from 0 to
4, x is from 0 to 3, y is from 0 to 3, z is from 0 to 4, to obtain
a product wherein the Z/E ratio of HFC-1225ye is decreased relative
to the Z/E ratio of HFC-1225ye in said starting material.
[0010] If the olefin is made at high temperature using a catalyst
that will equilibrate the two, then they will be made as a mixture
with the ratio of the two depending on the temperature at which
they were made. If you have a catalyst to interconvert one to the
other you can change the ratio by changing the temperature. For
example, if you start with pure Z and you want to make E, you can
equilibrate them at 350.degree. C. and make about 10% E. If you
start at 10% E, which is the case when we make the two at
350.degree. C., you can increase the Z to 99% by interconverting
them at 25.degree. C. using the claimed catalyst. Therefore, you
can approach the equilibrium composition from either side.
[0011] The foregoing general description and the following detailed
description are exemplary and explanatory only and are not
restrictive of the invention, as defined in the appended
claims.
DETAILED DESCRIPTION
[0012] Before addressing details of embodiments described below,
some terms are defined or clarified.
[0013] HFC-1225ye may exist as one of two configurational isomers,
E or Z. HFC-1225ye as used herein refers to the isomers,
E-HFC-1225ye (CAS reg no. 5595-10-8) or Z-HFC-1225ye (CAS reg. no.
5528-43-8), as well as any combinations or mixtures of such
isomers.
[0014] The term "Z/E ratio" is intended to mean the molar ratio of
Z isomer to E isomer of an olefin. For example, the term "Z/E ratio
of HFC-1225ye" is intended to mean the molar ratio of Z-HFC-1225ye
to E-HFC-1225ye.
[0015] The term "an elevated temperature" is intended to mean a
temperature higher than room temperature.
[0016] As used herein, the terms "comprises," "comprising,"
"includes," "including," "has," "having" or any other variation
thereof, are intended to cover a non-exclusive inclusion. For
example, a process, method, article, or apparatus that comprises a
list of elements is not necessarily limited to only those elements
but may include other elements not expressly listed or inherent to
such process, method, article, or apparatus. Further, unless
expressly stated to the contrary, "or" refers to an inclusive or
and not to an exclusive or. For example, a condition A or B is
satisfied by any one of the following: A is true (or present) and B
is false (or not present), A is false (or not present) and B is
true (or present), and both A and B are true (or present).
[0017] Also, use of "a" or "an" are employed to describe elements
and components described herein. This is done merely for
convenience and to give a general sense of the scope of the
invention. This description should be read to include one or at
least one and the singular also includes the plural unless it is
obvious that it is meant otherwise.
[0018] Unless otherwise defined, all technical and scientific terms
used herein have the same meaning as commonly understood by one of
ordinary skill in the art to which this invention belongs. Although
methods and materials similar or equivalent to those described
herein can be used in the practice or testing of embodiments of the
present invention, suitable methods and materials are described
below. All publications, patent applications, patents, and other
references mentioned herein are incorporated by reference in their
entirety, unless a particular passage is cited. In case of
conflict, the present specification, including definitions, will
control. In addition, the materials, methods, and examples are
illustrative only and not intended to be limiting.
[0019] A process has been provided to increase the Z/E ratio of
1,2,3,3,3-pentafluoropropene. The process comprises: contacting a
starting material comprising 1,2,3,3,3-pentafluoropropene with a
catalyst on AlF.sub.3 or carbon, wherein said catalyst is selected
from the group consisting of SbCl.sub.wF.sub.5-w,
TiCl.sub.xF.sub.4-x, SnCl.sub.yF.sub.4-y and TaCl.sub.zF.sub.5-z
wherein w is from 0 to 4, x is from 0 to 3, y is from 0 to 3, z is
from 0 to 4, to obtain a product wherein the Z/E ratio of
1,2,3,3,3-pentafluoropropene is increased relative to the Z/E ratio
of 1,2,3,3,3-pentafluoropropene in said starting material.
[0020] A process has also been provided to decrease the Z/E ratio
of 1,2,3,3,3-pentafluoropropene. The process comprises: contacting
a starting material comprising 1,2,3,3,3-pentafluoropropene with a
catalyst on AlF.sub.3 or carbon, wherein said catalyst is selected
from the group consisting of SbCl.sub.wF.sub.5-w,
TiCl.sub.xF.sub.4-x, SnCl.sub.yF.sub.4-y and TaCl.sub.zF.sub.5-z
wherein w is from 0 to 4, x is from 0 to 3, y is from 0 to 3, z is
from 0 to 4, to obtain a product wherein the Z/E ratio of
1,2,3,3,3-pentafluoropropene is decreased relative to the Z/E ratio
of 1,2,3,3,3-pentafluoropropene in said starting material.
[0021] Many aspects and embodiments have been described above and
are merely exemplary and not limiting. After reading this
specification, skilled artisans appreciate that other aspects and
embodiments are possible without departing from the scope of the
invention.
[0022] Other features and benefits of any one or more of the
embodiments will be apparent from the following detailed
description, and from the claims.
[0023] AlF.sub.3 can be made according to Journal of Fluorine
Chemistry, 125, 1169-1172 (2004), which is incorporated herein by
reference.
[0024] Carbon from any of the following sources are useful for the
embodiments of this invention: wood, peat, coal, coconut shells,
bones, lignite, petroleum-based residues and sugar. Commercially
available carbons which may be used include those sold under the
following trademarks: Barneby & Sutcliffe.TM., Darco.TM.,
Nucharm, Columbia JXN.TM., Columbia LCK.TM., Calgon PCB, Calgon
BPL.TM., Westvaco.TM., Norit.TM., and Barnaby Cheny NB.TM..
[0025] Carbon includes unwashed and acid-washed carbon (e.g.,
carbon which has been treated with hydrochloric acid or
hydrochloric acid followed by hydrofluoric acid). Acid treatment is
typically sufficient to provide carbon that contains less than 1000
ppm of ash. Suitable acid treatment of carbon is described in U.S.
Pat. No. 5,136,113, incorporated herein by reference. The carbon
also includes three dimensional matrix porous carbonaceous
materials. Examples are those described in U.S. Pat. No. 4,978,649,
incorporated herein by reference. In one embodiment of the
invention, carbon includes three dimensional matrix carbonaceous
materials which are obtained by introducing gaseous or vaporous
carbon-containing compounds (e.g., hydrocarbons) into a mass of
granules of a carbonaceous material (e.g., carbon black);
decomposing the carbon-containing compounds to deposit carbon on
the surface of the granules; and treating the resulting material
with an activator gas comprising steam to provide a porous
carbonaceous material. A carbon-carbon composite material is thus
formed.
[0026] Preparation of SbF.sub.5 on AlF.sub.3 has been described by
Quan et al. in Journal of Fluorine Chemistry, 125, 1169-1172
(2004).
[0027] Preparation of SbCl.sub.wF.sub.5-w, on AlF.sub.3 is
generally described in Examples 1 and 2. Preparation of
TiCl.sub.xF.sub.4-x on AlF.sub.3 is generally described in Example
3. Preparation of SnCl.sub.yF.sub.4-y on AlF.sub.3 is generally
described in Example 4. Preparation of TaCl.sub.zF.sub.5-z on
AlF.sub.3 is generally described in Example 5.
[0028] Preparation of SbCl.sub.wF.sub.5-w on carbon is generally
described in Examples 6 and 7. Preparation of TiCl.sub.xF.sub.4-x
on carbon is generally described in Example 8. Preparation of
SnCl.sub.yF.sub.4-y on carbon is generally described in Example 9.
Preparation of TaCl.sub.zF.sub.5-z on carbon is generally described
in Example 10.
[0029] The contac time of HFC-1225ye with the catalyst typically
ranges from about 1 second to 1 hour. In one embodiment of the
invention, the contac time ranges from about 5 seconds to 60
seconds.
[0030] The pressure employed in the isomerization process can be
subatmospheric, atmospheric or superatmospheric. In one embodiment
of the invention, the isomerization pressure is near atmospheric.
In another embodiment of the invention, the isomerization pressure
is autogenous.
[0031] The reactor for the the isomerization process and its
associated feed lines, effluent lines, and associated units used in
applying the processes of embodiments of this invention should be
constructed of materials resistant to corrosion. Typical materials
of construction include stainless steels, in particular of the
austenitic type, the well-known high nickel alloys, such as
Monel.TM. nickel-copper alloys, Hastelloy.TM. nickel-based alloys
and, Inconel.TM. nickel-chromium alloys, and copper-clad steel.
[0032] In a process to increase the Z/E ratio of HFC-1225ye, the
HFC-1225ye in the starting material is either E-HFC-1225ye or a
mixture of E-HFC-1225ye and Z-HFC-1225ye. The HFC-1225ye in the
starting material has a lower Z/E ratio than the HFC-1225ye in the
product.
[0033] In a process to increase the Z/E ratio of HFC-1225ye, the
temperature employed typically ranges from about -20.degree. C. to
about 150.degree. C. In one embodiment of the invention, the
temperature employed in the process to increase the Z/E ratio of
HFC-1225ye ranges from about -10.degree. C. to 100.degree. C. In
another embodiment of the invention, the temperature employed in
the process to increase the Z/E ratio of HFC-1225ye ranges from
about 0.degree. C. to 50.degree. C. In another embodiment of the
invention, the process to increase the Z/E ratio of HFC-1225ye is
conducted at about room temperature.
[0034] In a process to increase the Z/E ratio of HFC-1225ye, the
product has a higher Z/E ratio of HFC-1225ye than the starting
material. In one embodiment of the invention, the Z/E ratio of
HFC-1225ye in the product is at least 10. In another embodiment of
the invention, the Z/E ratio of HFC-1225ye in the product is at
least 20. In another embodiment of the invention, the Z/E ratio of
HFC-1225ye in the product is at least 40.
[0035] In a process to decrease the Z/E ratio of HFC-1225ye, the
HFC-1225ye in the starting material is either Z-HFC-1225ye or a
mixture of E-HFC-1225ye and Z-HFC-1225ye. The HFC-1225ye in the
starting material has a higher Z/E ratio than the HFC-1225ye in the
product.
[0036] In a process to decrease the Z/E ratio of HFC-1225ye, the
process is typically conducted at an elevated temperature. In one
embodiment of the invention, the process is conducted at a
temperature from about 300.degree. C. to 450.degree. C. Without
wishing to be bound by the theory, it is understood that the
isomerization between E-HFC-1225ye and Z-HFC-1225ye is an
equilibrium reaction. It is also understood that Z-HFC-1225ye is
thermodynamically more stable than E-HFC-1225ye, and the Z/E ratio
can be increased by decreasing the temperature in presence of the
claimed catalysts.
EXAMPLES
[0037] The concepts described herein will be further described in
the following examples, which do not limit the scope of the
invention described in the claims.
[0038] Examples 1-10 demonstrate the preparation of the
catalysts.
Example 1
[0039] Example 1 demonstrates the preparation of
SbCl.sub.wF.sub.5-w (w=0 to 4) on AlF.sub.3. Twenty five grams of
AlF.sub.3.3H.sub.2O (12/20 mesh) is heated for 10 hours at
300.degree. C. under a purge of nitrogen (10 sccm,
1.7.times.10.sup.-7 m.sup.3/s). Under an inert atmosphere, the
AlF.sub.3 is transferred to a glass round bottom flask and 25 gm of
SbCl.sub.5 is slowly dripped onto the powder. Periodic mixing with
a Teflon.RTM. paddle is carried out to infuse the mixture. Under an
inert atmosphere, the SbCl.sub.5 on AlF.sub.3 is transferred to
5/8'' Inconel tube for treatment with HF. The catalyst is heated
under a flow of nitrogen (20 sccm, 3.3.times.10.sup.-7 m.sup.3/s)
for three hours at 100.degree. C. Anhydrous HF (50 sccm,
6.0.times.10.sup.-7 m.sup.3/s) and N.sub.2 (50 sccm,
6.0.times.10.sup.-7 m.sup.3/s) are passed over the catalyst at
200.degree. C. for 2 hours and then only HF (100 sccm,
1.2.times.10.sup.-6 m.sup.3/s) for 3 hours. The temperature is
lowered to ambient and N.sub.2 (50 sccm, 6.0.times.10.sup.-7
m.sup.3/s) is passed over the catalyst for 8 hours.
Example 2
[0040] Example 2 demonstrates the preparation of
SbCl.sub.wF.sub.5-w (w=0 to 4) on AlF.sub.3. This catalyst is
prepared as described in Example 1 except 18.3 gm of SbF.sub.5 are
used in place of the SbCl.sub.5 and HF treatment is optional
Example 3
[0041] Example 3 demonstrates the preparation of
TiCl.sub.xF.sub.4-x (x=0 to 3) on AlF.sub.3. This catalyst is
prepared as described in Example 1 except 15.9 gm of TiCl.sub.4 is
used instead of SbCl.sub.5.
Example 4
[0042] Example 4 demonstrates the preparation of
SnCl.sub.yF.sub.4-y (y=0 to 3) on AlF.sub.3. This catalyst is
prepared as described in Example 1 except 22.0 gm of SnCl.sub.4 is
used instead of SbCl.sub.5.
Example 5
[0043] Example 5 demonstrates the preparation of
TaCl.sub.2F.sub.5-z (z=0 to 4) on AlF.sub.3. AlF.sub.3 pellets (20
gm) ground to 12/20 mesh are dried in a flow of N.sub.2 (50 sccm,
6.0.times.10.sup.-7 m.sup.3/s) for 10 hours at 300.degree. C. Under
an inert atmosphere, the pellets are transferred to a 1 L Hastelloy
C rocker bomb containing TaCl.sub.5 (30.1 gm). The rocker bomb is
cooled and anhydrous HF (200 gm) is added via vacuum transfer. The
mixture is heated to 50.degree. C. for four hours while rocking and
then the HF and HCl are vented to a scrubber. Under a nitrogen
blanket the solid is removed from the rocker bomb and transferred
to the Inconel reactor described in Example 1. Anhydrous HF (50
sccm, 6.0.times.10.sup.-7 m.sup.3/s) and N.sub.2 (50 sccm,
6.0.times.10.sup.-7 m.sup.3/s) are passed over the catalyst at
80.degree. C. for 2 hours and then only HF (100 sccm,
1.2.times.10.sup.-6 m.sup.3/s) for 3 hours. The temperature is
lowered to ambient and N.sub.2 (50 sccm, 6.0.times.10.sup.-7
m.sup.3/s) is passed over the catalyst for 8 hours.
Example 6
[0044] Example 6 demonstrates the preparation of
SbCl.sub.wF.sub.5-w (w=0 to 4) on carbon. Acid washed coconut shell
carbon (6.times.10 mesh, 10 gm) as described in U.S. Pat. No.
5,136,113 is heated for 10 hours at 300.degree. C. under a purge of
nitrogen (10 sccm, 1.7.times.10.sup.-7 m.sup.3/s). Under an inert
atmosphere, the carbon particles are transferred to a glass round
bottom flask and 25 gm of SbCl.sub.5 is slowly dripped onto the
powder. Periodic mixing with a Teflon.RTM. paddle is carried out to
infuse the mixture. Under an inert atmosphere, the SbCl.sub.5 on
carbon is transferred to 5/8'' Inconel tube for treatment with HF.
The catalyst is heated under a flow of nitrogen (20 sccm,
3.3.times.10.sup.-7 m.sup.3/s) for three hours at 100.degree. C.
Anhydrous HF (50 sccm, 6.0.times.10.sup.-7 m.sup.3/s) and N.sub.2
(50 sccm, 6.0.times.10.sup.-7 m.sup.3/s) are passed over the
catalyst at 200.degree. C. for 2 hours and then only HF (100 sccm,
1.2.times.10.sup.-6 m.sup.3/s) for 3 hours. The temperature was
lowered to ambient and N.sub.2 (50 sccm, 6.0.times.10.sup.-7
m.sup.3/s) was passed over the catalyst for 8 hours.
Example 7
[0045] Example 7 demonstrates the preparation of
SbCl.sub.wF.sub.5-w (w=0 to 4) on carbon. This catalyst is prepared
as described in Example 6 except 18.3 gm of SbF.sub.5 are used in
place of the SbCl.sub.5 and HF treatment is not required.
Example 8
[0046] Example 8 demonstrates the preparation of
TiCl.sub.xF.sub.4-x (x=0 to 3) on carbon. This catalyst is prepared
as described in Example 6 except 15.9 gm of TiCl.sub.4 is used
instead of SbCl.sub.5.
Example 9
[0047] Example 9 demonstrates the preparation of
SnCl.sub.yF.sub.4-y (y=0 to 3) on AlF.sub.3. This catalyst is
prepared as described in Example 6 except 22.0 gm of SnCl.sub.4 is
used instead of SbCl.sub.5.
Example 10
[0048] Example 10 demonstrates the preparation of
TaCl.sub.zF.sub.5-z (z=0 to 4) on carbon. Acid washed coconut shell
carbon (6.times.10 mesh, 10 gm) as described in U.S. Pat. No.
5,136,113 is dried in a flow of N.sub.2 (50 sccm,
6.0.times.10.sup.-7 m.sup.3/s) for 10 hours at 300.degree. C. Under
an inert atmosphere, the particles are transferred to a 1 L
Hastelloy C rocker bomb containing TaCl.sub.5 (30.1 gm). The rocker
bomb is cooled and anhydrous HF (200 gm) is added via vacuum
transfer. The mixture is heated to 50.degree. C. for four hours
while rocking and then the HF and HCl are vented to a scrubber.
Under a nitrogen blanket the solid is removed from the rocker bomb
and transferred to the Inconel reactor described in Example 1.
Anhydrous HF (50 sccm, 6.0.times.10.sup.-7 m.sup.3/s) and N.sub.2
(50 sccm, 6.0.times.10.sup.-7 m.sup.3/s) are passed over the
catalyst at 80.degree. C. for 2 hours and then only HF (100 sccm,
1.2.times.10.sup.-6 m.sup.3/s) for 3 hours. The temperature is
lowered to ambient and N.sub.2 (50 sccm, 6.0.times.10.sup.-7
m.sup.3/s) is passed over the catalyst for 8 hours.
[0049] Examples 11-18 describe the isomerization processes of
HFC-1225ye in the presence of the catalysts.
Example 11
[0050] Example 11 demonstrates the isomerization of E-HFC-1225ye to
Z-HFC-1225ye.
[0051] To a 15''.times.5/8'' OD Inconel reactor is added 10 cc of
SbX.sub.5 (where X is Cl or F) on AlF.sub.3 prepared as described
in Example 1. E-HFC-1225ye (20 sccm, 3.3.times.10.sup.-7 m.sup.3/s)
is passed over the catalyst at room temperature, and the reactor
effluent is analyzed by GC-MS and found to contain
Z-HFC-1225ye.
Example 12
[0052] This is similar to Example 11 except TiX.sub.4 catalyst is
used as described in Example 3.
Example 13
[0053] This is similar to Example 11 except SnX.sub.4 catalyst is
used as described in Example 4.
Example 14
[0054] This is similar to Example 11 except TaX.sub.5 catalyst is
used as described in Example 5.
Example 15
[0055] This is similar to Example 11 except SbX.sub.5 catalyst is
used as described in Example 7.
Example 16
[0056] This is similar to Example 11 except TiX.sub.4 catalyst is
used as described in Example 8.
Example 17
[0057] This is similar to Example 11 except SnX.sub.4 catalyst is
used as described in Example 9.
Example 18
[0058] This is similar to Example 11 except TaX.sub.5 catalyst is
used as described in Example 10.
[0059] Note that not all of the activities described above in the
general description or the examples are required, that a portion of
a specific activity may not be required, and that one or more
further activities may be performed in addition to those described.
Still further, the order in which activities are listed are not
necessarily the order in which they are performed.
[0060] In the foregoing specification, the concepts have been
described with reference to specific embodiments. However, one of
ordinary skill in the art appreciates that various modifications
and changes can be made without departing from the scope of the
invention as set forth in the claims below. Accordingly, the
specification and figures are to be regarded in an illustrative
rather than a restrictive sense, and all such modifications are
intended to be included within the scope of invention.
[0061] Benefits, other advantages, and solutions to problems have
been described above with regard to specific embodiments. However,
the benefits, advantages, solutions to problems, and any feature(s)
that may cause any benefit, advantage, or solution to occur or
become more pronounced are not to be construed as a critical,
required, or essential feature of any or all the claims.
[0062] It is to be appreciated that certain features are, for
clarity, described herein in the context of separate embodiments,
may also be provided in combination in a single embodiment.
Conversely, various features that are, for brevity, described in
the context of a single embodiment, may also be provided separately
or in any subcombination. Further, reference to values stated in
ranges include each and every value within that range.
* * * * *